Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
  • C08K5/34928—Salts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/5205—Salts of P-acids with N-bases

Definitions

• the invention relates to aids for preventive fire protection. These are a combination of at least two substances, one of which is an ethylenediamine phosphate and a second melamine and / or a salt of a cyanuric acid derivative.
• Such tools for fire protection are e.g. in the case of flame, foaming and forming a fire-repellent and insulating foam, if appropriate thermoplastic processes, which are obtained by incorporating a powdery filler consisting of a mixture of ethylenediamine phosphate and cyanuric acid derivatives in thermoplastics at temperatures below 210 ° C.
• the invention furthermore relates to moldings made from thermoplastics modified in this way.
• Intumescent materials are materials which, for example, form a fire-repellent and more or less good heat insulating foam made of organic and / or inorganic material when exposed to flame.
• Thermoplastically processable plastics with an intumescent character and, for example, rubber-elastic properties have not yet been introduced, although there is a great technical need (e.g. for sealing materials, covers or other structural elements in the technical area of preventive fire protection).
• intumescence-mediating active substance combinations have almost all hygroscopic properties, which can lead to severe restrictions in the use properties of the base materials equipped with them.
• Many such combinations of intumescent substances decompose at temperatures above 120 ° C, which hinders their incorporation into thermoplastics, which usually require temperatures between 100 and 200 ° C.
• intumescence-mediating active substance combinations after incorporation into higher molecular weight base materials for example thermoplastic plastics, elastomers
• E thylendiaminphosphat has been proposed as for fire prevention excellently suitable phosphate (DE-OS 2,938,874). It is not hygroscopic, reacts neutrally and already provides an intumescent foam when exposed to flame.
• ethylenediamine phosphate is particularly suitable, e.g. as an additive to thermoplastics to impart these inumescent properties.
• Melamine phosphate itself is not suitable for this purpose because it alone has no intumescent properties. It is only suitable to impart a certain fire resistance to thermoplastics and has already been used for this purpose. Furthermore, melamine phosphate reacts strongly acidic (pH 2-3) due to hydrolysis, which is often undesirable.
• thermoplastic transfer processable rubber-like (ie elastomeric), or hard or plastic plastics in solid, porous or foamed intumescent materials.
• the combinations according to the invention include combinations of melamine and ethylene amine diphosphate as well as combinations of salts of melamine, preferably melamine phosphate and ethylene amine diphosphate.
• a combination of the invention by, for example, reacts equally ethylenediamine and M elaminphosphat (1.4 mole of melamine + 1 mole of H 3 P0 4) close to neutral (pH 6.5) and gives a wide variety of substrates intumescent as is the inventive combination of ethylene diamine / melamine, although the melamine phosphate itself does not mediate intumescence.
• thermoplastically processable polymers or polymeric or oligomeric materials with intumescent properties which are characterized in that they contain an intumescent mediating active ingredient mixture of ethylenediamine phosphate and optionally cyanuric acid or its derivatives and / or its salts incorporated.
• thermoplastically processable polymers or polymeric or oligomeric materials with intumescent properties are thereby known according to the invention records that they contain a powdery mixture of ethylenediamine phosphate and optionally melamine and / or melamine salts and ethylenediamine phosphate contents above 10 wt .-% incorporated and the powdery mixture makes up more than 40 wt .-% of the polymer with intumescent properties.
• mixtures according to the invention have a low tendency to "boil” and melt the substrate in the event of flaming, which is a fire protection advantage since a better carbonization layer can be formed in this way.
• the present invention relates to a method for producing intumescent materials, e.g. Mortar, putty, varnish, coatings, film, hard or flexible, thermoplastic or thermoset molded parts, which are obtained by using appropriate substrates, e.g. inorganic or in particular organic binders, lacquers, rubber mixtures, thermoplastics or thermosets at a suitable point in time before the final processing, combinations of ethylenediamine phosphate and cyanuric acid or their derivatives or their salts, such as melamine (phosphate), mixed in or produced in them.
• substrates e.g. inorganic or in particular organic binders, lacquers, rubber mixtures, thermoplastics or thermosets at a suitable point in time before the final processing, combinations of ethylenediamine phosphate and cyanuric acid or their derivatives or their salts, such as melamine (phosphate), mixed in or produced in them.
• intumescent materials i.e. intumescent powders, granules or coatings can be used.
• the combinations according to the invention can be admixed, for example, with plastic latices or lacquer solutions. Coatings and intumescent properties can be produced from these Provide coated materials with protection against flame.
• the mixture according to the invention can be mixed into one or both components of polyester resins or epoxy resins with equal success. It can be added to thermoplastics or rubbers that can be processed at temperatures of 150 - 200 ° C and then receives, for example, films or extrudates with intumescent properties that are used in the field of preventive fire protection.
• thermoplastically processable materials and molded parts based on polymers with intumescent properties have excellent fire technology properties and are halogen-free.
• the pure polymers are considered as brittle-hard, hard-tough, plastic or elastic polymers or polymeric materials to be processed thermoplastically, but also polymer mixtures or copolymers, graft polymers, graft copolymers, block polymers and their mixed forms, and also with plasticizers, fillers, fibers, Pigments, active ingredients modified polymers. It can be aromatic, aliphatic, araliphatic, heterocyclic polyaddition, polycondensation, polyoxidation or vinyl polymers and their mixed forms.
• Examples include polyurethanes, polyureas, polycarbodiimides, polyethers, polyether esters, Polyimides, polysulfones, polysulfides, polyoxides, polyamides, polyamines, polyvinyl esters, polyvinyl halides, polyvinyl aromatics, polymethacrylates, polyacrylates, polydiolefins, polyolefins or copolymer forms and mixed forms of these types of polymers.
• Polymers which are very suitable in this sense are, for example, polyurethanes based on aliphatic and / or aromatic polyisocyanates and polyester or polyether polyols, vinyl acetate (mixed) polymers, vinyl chloride (mixed) polymers, aliphatic and / or partially aromatic polyesters and polyamides, polyolefins, or their elastic or plastic copolymers.
• Examples include polyadducts of tolylene diisocyanate and / or diphenylmethane diisocyanate and / or hexamethylene diisocyanate and adidpic acid polyesters and / or ethylene oxide / propylene oxide polyethers, copolymers of vinyl chloride and vinyl acetate with optionally further vinyl monomers, butadiene-styrene copolymers, ethylene copolymers or block copolymers - (Block) copolymers, ethylene-ethyl acrylate copolymers, ethylene-vinyl acetate copolymers, homopolymers and copolymers of styrene, polyethylene, polypropylene, polyisobutylene, methyl methacrylate and its copolymers.
• ethylenediamine phosphate is understood primarily as the neutralization product of ethylenediamine and orthophosphoric acid.
• this amine phosphate is advantageous to use this amine phosphate as a phosphate component of the intumescence-mediating active substance mixture, since it reacts neutrally.
• ammonium phosphates in particular ammonium polyphosphates, which are known as a phosphate component of intumescent materials
• hydrolytic influences to which an intumescent material is often exposed in practice can form excess acid from the polyphosphate, which can give rise to corrosion.
• the polymer with intumescent properties should contain at least 10% by weight of ethylenediamine phosphate. Up to 100% by weight of phosphate alone can also serve as intumescent agents.
• Cyanuric acid and / or its derivatives or derivatives, ie cyanuric acid or compounds which can be understood as cyanuric acid or isocyanic acid arrivals, are optionally used as a further constituent of the active compound mixture.
• Examples include urazoles, melamine urazolate, cyanamide, dicyanamide, dicyandiamide, amelide, melamine cyanurate, cyanuric acid salts and cyanuric acid ester and amides, and salts of cyanuric acid derivatives such as Cyanamide, dicyanamide, hydrazodicarbonamide, dicyandiamide, guanidine and salts thereof, biguanide, urazole, Urazolcyanurat, melamine cyanurate, cyanuric acid salts and C yanurklar and amides, in particular melamine and / or its which is preferred because of its good accessibility salts.
• the base body 2,4,6-triamino-s-triazine is preferably understood to be melamine, but e.g. also to consider its condensation products obtainable by thermal conditions or reaction with formaldehyde.
• urea, guanidine, allophanate, biurett, dicyandiamide, their polycondensation products and primarily their water-insoluble, if appropriate acid or base-modified formaldehyde condensation products or their salts are also to be included.
• melamine is preferably used as the cyanuric acid derivative.
• salt formation can take place using basic components such as ammonia, amines, alkali metal, alkaline earth metal, earth metal ions or other inorganic and organic bases.
• base reacting cyanuric acid derivatives it can be carried out using organic or inorganic acidic components, for example trimellitic acid, pyromellitic acid, malonic acid, citric acid, oxalic acid, trichloroacetic acid, HCl, Sulfuric acids, sulfonic acids, nitric acid, boric acid, but in particular with acids based on phosphorus, for example orthophosphoric acid and their various dehydration products, such as pyro-, meta- or polyphosphoric acid, phosphoric acid, phosphonic acids, phosphinic acids, etc.
• melamine phosphate melamine oxalate, melamine acetate
• mixed salts such as melamine phosphate
• Salt formation can be stoichiometric, over-stoichiometric or preferably sub-stoichiometric, e.g. in which less than one mole of orthophosphoric acid is used for salt formation per mole of melamine.
• phosphates of the melamine phosphate type are preferably understood to mean reaction products of 1 mol of melamine with 0.01 to 2.5, preferably 0.1 to 1.0 mol of orthophosphoric acid.
• Other phosphoric acids such as meta, pyro or polyphosphoric acid or those with other valence levels of the phosphorus can also be considered.
• the phosphates are prepared, for example, by reacting melamine with H 3 PO 4 in aqueous suspension at 10-120 ° C., cooling, filtering and drying. Mixtures of melamine with melamine phosphates with a high phosphoric acid content can be used instead of melamine phosphates with a low phosphoric acid content.
• those phosphates are also referred to as "phosphates of the melamine phosphate type" which are soluble in water below 5% by weight, preferably below 1% by weight (in the form of the saturated solution at room temperature) and optionally by addition from e.g. Phosphoric acids are formed on cyanuric acid derivatives, e.g.
• cyanamide, dicyanamide, hydrazodicarbonamide, dicyandiamine, guanidine biguanide, urazole, urazol cyanurate, melamine cyanurate, cyanuric acid salts and cyanuric acid esters and amides, crosslinked or uncrosslinked formaldehyde condensates of urea, melamine, dicyandiamide, but melanin, guanidine, particularly preferred because of its good properties, guanidine, guanidine, guanidine, guanidine guanidine .
• Mixtures of different salts or cyanuric acid derivatives can also be used.
• the proportion of ethylenediamine phosphate in the at least two-component mixture should be at least 1%, preferably 5-95% by weight, preferably 10-75% by weight.
• the mixture components can be used in premixed form, for example when salts are used in a single stage after they have been prepared together Neutralization or manufacturing process, by grinding the finished salts together or, for example, by simply mixing prefabricated salts.
• the mixture components can also be added in succession in the case of formulations, for example fire protection putty or polymer blends.
• a single or joint production in a binder from the components capable of salt formation in situ can also be considered.
• the individual components are preferably added in the form of a finished premix or separately in succession.
• the mixture according to the invention is used as an intumescence-imparting active ingredient itself or incorporated into a binder.
• binders are primarily oligomeric or polymeric materials, or solutions, dispersions, suspensions, mixtures or melts, powders or granules.
• Natural binders such as protein, gelatin, casein, starches, dextrans, digested cellulose, for example methyl or ethyl or oxyethyl or carboxymethyl cellulose in the form of their aqueous solutions, rubber latices, latices of polyurethanes or vinyl polymers such as polyvinyl acetate or polyvinyl chloride or latices containing polyvinyl acetate or Solutions.
• Coating resins and solutions such as alkyd resins, C yclokatuschuke, chlorinated rubbers, paints Based on unsaturated fatty acid condensates, polyesters, polyethers, polyurethanes, epoxides, polyamides, polyimides, polymethylols, thermoplastics such as polystyrenes, polyolefins, such as polyethylene, polypropylene, polybutene, polychloroprene, olefin copolymers, such as ethylene vinyl acetate copolymers, ethylene copolymers with (meth) acrylic acid and / or (meth) acrylic acid and their esters, styrene-butadiene block polymers, or polyolefin rubbers, phenolic resins, melamine resins, urea resins, silicone resins, or rubbers; Thermosets such as epoxy resins, polyurethane resins, F uranium resins, polyacrylate resins,
• the incorporation of the salt mixture according to the invention leads to materials and later molded parts, coatings or construction elements which are characterized by the halogen-free intumescent mixture and good fire resistance with good intumescent behavior under flaming.
• the intumescent behavior can be largely influenced proportionally with the content of ethylenediamine phosphate in the salt mixture.
• the intumescent materials should contain 5-95% by weight, preferably 20-95, in particular 40-80% by weight, of the mixture according to the invention. In general, at least 30% of the mixture as part of the intumescent material should be aimed for in order to achieve good intumescence with good fire resistance.
• the active substance mixture imparting intumescent properties to be incorporated into the polymers may also contain other fillers, pigments, coloring components, odorants, lubricants, stabilizers, blowing agents, fibers, crosslinking agents, plasticizers, halogen-containing or halogen-free, antimony or boron-containing additional flame retardants, e.g. Fillers, hollow pearls, pigments, plasticizers, stabilizers, reinforcing fibers, thickeners, plasticizers, lubricants, solvents and diluents, etc.
• additional flame retardants e.g. Fillers, hollow pearls, pigments, plasticizers, stabilizers, reinforcing fibers, thickeners, plasticizers, lubricants, solvents and diluents, etc.
• They can be used as paints or paints, coatings or coating agents, as casting resins or molded parts, as thermoplastic or Vulcanizable rubbers, or more or less flexible molded parts, can be used as hard or soft materials that can be processed thermoplastically, or molded articles that can be produced by pressing, extruding, injection molding, deep drawing, calendering or other heat deformation processes. They can be part of mortars or putties, sealants or adhesives.
• the active ingredient mixture can be wholly or partly mixed into the polymer during production, during workup or during any necessary mixing or formulation steps, auxiliary solvents being able to be used.
• the active ingredient mixture can e.g. together with plasticizers such as Adipic acid esters, phthalic acid esters, phosphonic acid esters, PVC or elastomer mixtures are added.
• the active ingredient mixture is usually admixed with the polymer to be processed thermoplastically on the roller or in a mixing drum or on kneaders or screw machines at temperatures between 20 and 220 ° C., preferably 100-180 ° C. It is advantageous here if the active substance mixture is in granular form or preferably as a powder which has been sieved to a degree of at least 95% by weight through a sieve with a mesh size of 0.125 mm.
• thermoplastically processable polymers accessible according to the invention can be prepared by conventional thermoplastic processing methods, e.g. processed by rolling, extruding, blowing, pressing, deep-drawing, spraying, sintering into foils, plates, profiles, tubes, profiles of various designs or other shaped bodies. Polymers or processing methods are preferred which allow working at temperatures below 300 ° C., preferably at temperatures below 220 ° C.
• elastomers e.g. Equip olefin copolymers such as ethylene-vinyl acetate copolymers on rollers with the active compound mixture according to the invention at temperatures below 180 ° C., or process them into films, tapes and profiles.
• the films, profiles, moldings produced in this way are used in the field of preventive fire protection, it being advantageous that the moldings not only have an intumescent effect in the event of a fire, but are in many cases flame-retardant or self-extinguishing due to the active ingredient content according to the invention.
• the polymer preparations according to the invention are used to produce a wide variety of articles for preventive fire protection, such as Films, and if necessary tapes equipped with adhesives, reinforcing fibers or fabrics or metal foils for covering or wrapping electrical cables or pipes, for producing cable sheaths, pipes and seals, or molded parts in the field of air conditioning, sound insulation, electrical, insulation or installation .
• articles for preventive fire protection such as Films, and if necessary tapes equipped with adhesives, reinforcing fibers or fabrics or metal foils for covering or wrapping electrical cables or pipes, for producing cable sheaths, pipes and seals, or molded parts in the field of air conditioning, sound insulation, electrical, insulation or installation .
• they serve, for example, as joint profiles, sealing profiles for doors, windows or wall joints, floors or ceilings, hollow molds, housings for components to be protected, devices, systems or flexible or rigid covers for machines and / or devices, which in turn are covered with fabrics, nonwovens, Support structures made of combustible or non-combustible material in the form of sandwiches, Coatings, laminates, paints, etc. can be combined. They can be processed by gluing, welding, co-calendering, co-extruding, etc.
• Polymer K 1 Like polymer K, but with 20% by weight of a polyester composed of adipic acid, glycerin and glycol (OH number 250).
• Components A and B were incorporated in amounts of 75% by weight, based on the total mixture, on a kneading roll system at 160 ° C. into the rolled skin formed by the respective polymer. Only the polymer P was mixed with the components in the form of a 50% latex, dried and transferred to a rolled skin.
• the rolled skins were then pelletized and the pellets processed at 180 ° C. on a heated press into 5 mm thick press plates for test purposes.
• M model films were made into 1.5 mm thickness from the granules on a roll mill at about 170 ° C.
• test specimens with a base area of 20 x 30 mm and a height of 1.5 or 5 mm were placed in a circulating air cabinet preheated to 350 ° C and after 10 minutes the foaming was assessed (intumescence behavior).
• a volume increase of more than 200% with 1 and no volume increase with 6 and the corresponding volume increases in between were rated.
• a commercially available plastic-jacketed three-wire L ampentiv is cut into 20 cm long pieces (diameter of the cable about 7 mm). 10 cm of such a cable test piece are tightly sheathed with a film according to Example 3, the sheathing being fixed to a film tube by simply welding the film web by means of a soldering iron. Half of the cable piece is now provided with a protective sheath.
• the cable piece is now attached horizontally over a natural gas burner by clamping the cable cores on both sides in a tripod - and fixed in a horizontal position, so that the boundary between the covered and uncovered cable piece lies exactly above the center of the burner nozzle and the slot or flame of the burner B, both sides of the riding Jardinprüflings 3 cm wide sweeps. Then the burner flame is ignited. After 5 seconds the unprotected cable area burns with a strong flame, while the protected part shows only a medium amount of foaming without flame development. After 1 minute, the unprotected cable jacket has already burst and burns strongly, the protected part still has its original shape, only thickened by the foaming of the jacket.
• the experiment is stopped after 5 minutes: the unprotected part of the cable has burned down to the heavily discolored copper core and slag residues, while the protected part of the cable test specimen still has the functional, albeit charred, but still clearly preserved and functional geometry (3 cable cores with insulation contained in a cable sheath and sheath of the same).
• the copper core is still bare about 3 cm from the flame from the burner.
• a film according to Example 3 is laminated onto it by running it together with a glass fiber fabric over a calender heated to 150 ° C. Flame lamination is also possible here. Bands are cut from this approximately 1.5 mm thick film, which is now reinforced on one side with the glass fabric. These tapes are particularly suitable for wrapping pipes or cables or calf sheets to protect against fire.
• the flexible, elastic material can also be used to close wall openings can be seen as follows: A hole with an 8 cm diameter is drilled in a 10 cm thick foam block. A ball is inserted into this hole, which is obtained by crumpling up a A4-sized sheet of the glass fabric-reinforced film described above. This ball remains stuck in the hole due to its expandability. A Bunsen burner with a high lit flame is now placed under this hole. After 2 hours it is over the bunsen burner located shaft opening of the hole, which was closed with the ball, still closed against the passage of the burner flame. A plug of foamed and charred material has formed on the flame side.
• a tube with a wall thickness of 3 mm and a clearance of 15 mm is extruded from a material (as granulate) according to Example 5 at 190 ° C. on a screw machine and cut open parallel to the axis.
• the result is a tubular molding that can be pulled onto electrical cables and protects them from fire.
• This mass was processed in a silicone mold, possibly by repeated entry and drying at 50 ° C., to give test plates measuring 2x2x0.2 cm.
• test platelets were placed on a wire sieve with a mesh size of 2 mm and flame-treated from above at an angle of 45 ° with the tip of the flame cone of a lighted natural gas Bunsen burner.
• Salts of melamine (M) and H 3 PO 4 (P) in various molar ratios, abbreviated MP, are used here as salts of cyanuric acid derivatives.
• a salt mixture of 90 parts EDP and 10 parts MP (1: 0.15) is mixed with a 7.5% solution of cationic starch to give a coating color.
• 10 parts of Ti02 white pigment are added. This coating color is used to coat wallpaper papers approx. 1 mm thick. An intumescent coating is obtained, which makes the wallpaper suitable for wallcovering of endangered rooms.
• a wall that has already been papered can be painted with the coating formulation in a conventional manner in a fire-retardant manner.
• Example 8 22 parts of the salt mixture used in Example 8 are incorporated into 10 parts of a highly viscous silicone oil (oil M 300 000, Bayer AG). A putty is obtained which does not burn in the usual flame test and shows a volume expansion of 300%.
• Example 8 400 parts of the salt mixture used in Example 8 are incorporated into 100 parts of ethylene-vinyl acetate copolymer (vinyl acetate content approx. 45%) on a heating calender at 145 ° C. After removal from the roller, a flexible film (1.5 mm thick) is obtained. , which expands in the flame test without afterburning by 250 vol% without melting. The underlay is insulated against flame entry.
• Paper sleeves filled with such granulate serve as finished parts for the reversible closure of holes in fire walls, through which e.g. Cables are routed.
• Polyethylene bags or knitted hoses filled with this granulate are used for the reversible sealing of cable trays in fire compartments.
• Example 27 is repeated, but the amount of water is doubled and the salt paste is kneaded with 100 parts of mineral wool before drying. 20 parts of starch are also added. These granules form less Dust during processing and shows a better mechanical resistance of the intumescent foam with 300% volume expansion. It is used for fillings with fire protection.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Fireproofing Substances (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Organic Insulating Materials (AREA)

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Citations (3)

• 1982
  • 1982-08-03 DE DE19823228863 patent/DE3228863A1/de not_active Withdrawn
• 1983
  • 1983-07-22 EP EP83107178A patent/EP0104350A3/fr not_active Withdrawn
  • 1983-08-01 JP JP13954283A patent/JPS5947285A/ja active Pending

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